Substituted O-{8 aminosulfonyl{9 -glycolic anilides herbicides

ABSTRACT

New and valuable substituted O-(aminosulfonyl)-glycolic anilides and a process for controlling the growth of unwanted plants with these compounds.

United States Patent Fischer et al.

[ Dec. 30, 1975 SUBSTITUTED O-[AMINOSULFONYL]-GLYCOLIC ANILIDESHERBICIDES Inventors: Adolf Fischer, Mutterstadt; Gerhard Hamprecht,Mannheim; Dietrich Mangold, Neckargemuena; Wolfgang Rohr, Mannheim, allof Germany Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft,Ludwigshafen (Rhine), Germany Filed: Sept. 3, 1974 Appl, No.: 502,740

Related U.S. Application Data Division of Ser. No. 321,548, Jan. 5,1973, Pat. No. 3,870,740.

Foreign Application Priority Data Jan. 13, 1972 Germany 2201432 PrimaryExaminer-Lewis Gotts Assistant Examiner -Catherine L. Mills Attorney,Agent, or Firm.lohnston, Keil, Thompson & Shurtleff [57] ABSTRACT Newand valuable substituted O-[aminosu1fony1]- glycolic anilides and aprocess for controlling the growth of unwanted plants with thesecompounds.

2 Claims, No Drawings SUBSTITUTED O-[AMINOSULFONYL l-GLYCOLIC ANILIDESHERBICIDES This is a division of application Ser. No. 321,548, filedJan. 5, 1973, now U.S. Pat. No. 3,870,740.

The present invention relates to new and valuable substitutedO-[aminosulfonyl]-glycolic anilides, their preparation and use asherbicides.

It is known to use chloroacetic acid-N-isopropylanilide as a herbicide.However, its biological action is only moderate.

We have now found that substituted O-[aminosulfonyl]glycolic anilides ofthe formula -glycolic slender foxtail amaranth species wild oat bromespecies goosefoot species Alupvrcurux myoxumides llmaranllzux .rpp.

fatua Bmmus .s'pp. Clu'nupodium spp.

Darlylis glomeralu orchardgrass Digilariu .mnguinulis large crabgrassEchinnchloa crux-gall! barnyardgrass Eleuxine it died goosegrasscatchweed bedstraw deadnettle species ryegrass species chamomile panicum.i'pp. bluegrass species Solaria spp. foxtail species Sinapis arvenxixWild mustard without causing damage to the crop plants:

Allium cepa onions (ialium aparine Lamium spp.

Lalium .rpp. Malricaria chamomilla l'uniz'ium .i'pp.

Poa spp.

Bela rulgarix, beet' Brarsica .rpp. cabbage species Cucumrlr sum-uscucumbers Daucus carata carrots (ioxsypium liirsutum' COttOh Helium/msannuus sunflower Hordeum vulgare barley I Lacluca Spp. lettuce speciesLinum uxilalissimum flax M vdimgn saliva alfalfa Oryza .tatira ricePt'lmselinum .mlii'um parsley Pixum .talirum peas P/taxeolus spp beansSoja liixpr'da (Glycine max.)

Solarium ruhr'rns'um potatoes Spinacia oleracea spinach Sorghum bimlnrsorghum Trilicum aexlirum wheat Trifnlium .rpp. clover Application ratesare from 0.2 to 5 kg of active ingredicnt per hectare; the'compoundsmaybe applied before sowing, or before or after emergence of the plants.

The compounds of the invention may be prepared by reacting a substitutedglycolic anilide with a substituted aminosulfonyl chloride in thepresence of an acid acceptor, e. g., triethylamine and pyridine.

EXAMPLE 1 O-[isopropylaminosulfonyll-glycolic acid-N-butyn- 1-yl-3-anilide At to C and while stirring, a solution of 333 parts byweight of isopropylaminosulfonyl chloride in parts by weight ofdichloromethane was added to a solution of 35.5 parts by weight ofglycolic acid-N- butyn-l-yl-3-anilide and 21.4 parts by weight oftrieth- 5 ylamine in 600 parts by weight of dichloromethane.

After 2 hours the reaction mixture was successively washed with dilutehydrochloric acid, water, sodium bicarbonate solution, and again withwater, and then dried with magnesium sulfate. The crude product, meltingat 99 to C, was obtained from the organic phase upon concentration invacuo. The pure compound melting at 108 to 110C may be obtained byrecrystallization from benzene.

The compound has the following structural formula:

The following compounds were obtained analor gously:

glycolic acid-N-isopropylanilide, m.p. 59 to 60C glycolicacid-N-isobutylanilide, m.p. 53 to 54C glycolicacid-N-tert-butylanilide, mp 55 to 56C.

Glycolic anilides are obtained in the same manner by reacting, inaccordance with the scheme shown below, N-alkylanilines withl,3-dioxolane-2,4-dione (J. Chem. Soc., 1357, 1951). R and R have themeanings given above.

Glycolic acid-N-methylanilide A solution of 10.7 parts by weight ofN-methylaniline in 20 parts by weight of tetrahydrofuran has added toit, at to C and with stirring, a solution of 10.2 parts by weight ofl,3-dioxolane-2,4-dione in parts by weight of tetrahydrofuran. Thereaction mixture was then stirred at room temperature until no morecarbon dioxide evolved, and subsequently concentrated to dryness invacuo. The crude product obtained melts at 48 to 50C; the analyticallypure compound is obtained by recrystallization from ether; m.p.: 50 to52C.

The following compounds were obtained analogously: I

glycolic acid-N-ethylanilide, m.p. 39 to 41C glycolicacid-N-n-propylanilide, m.p. 68 to 69C glycolic acid-N-propargylanilide,m.p. 69 to 71C glycolic acid-N-3-methylbutyn-1-yl-3-anilide glycolicacid-N-allylanilide glycolic acid-N-buten-l-yl-3-anilide glycolicacid-N-3-methylbuten1-yl-3-anilide glycolic acid-N-cyclohexylanilideglycolic acid-N-cyclopentylanilide glycolic acid-N-benzylanilide.

The agents according to the invention may be used as solutions,emulsions, suspensions or dusts. The form of application dependsentirely on the purpose for which the agents are being used; in any caseit should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbonshaving boiling points higher than 150C, e.g. tetrahydronaphthalene oralkylated naphthalenes, or organic liquids having boiling points higherthan 150C and having one or more than one functional group, e.g. theketo group, the ether group, the ester group or the amide group, thisgroup or these groups being attached as substituent(s) to a hydrocarbonchain or being a component of a heterocyclic ring, may be used as sprayliquids.

Aqueous formulations may be prepared from emulsion concentrates, pastesor wettable powders by adding water. To prepare emulsions theingredients as such or dissolved in a solvent may be homogenized inwater or organic solvents by means of wetting or dispersing agents,e.g., polyethylene oxide adducts. Concentrates which are suitable fordilution with water may be prepared from active ingredient, emulsifyingor dispersing agent and possibly solvent.

Dusts may be prepared bymixing or grinding the active ingredients with asolid carrier, e.g., kieselguhr, talc, clay or fertilizers.

Granules may be prepared by applying the active ingredients to solidcarriers of various particle sizes.

Adherents, oils and other herbicidal active ingredients may also beadded.

EXAMPLE 2 In the greenhouse, loamy sandy soil was filled into pots andsown with Zea mays, Soja hispida, Gossypium hirsulum, Beta vulgaris,Echinochloa crus-galli, Setaria spp., Poa lrivialis, Bromus tectorum andAlopecurus myosuroides. The soil prepared in this manner was thentreated with 2 kg per hectare of O-(isopropylaminosulfonyl)-glycolicacid-N-butyn-1-yl-3-anilide (l) and, for comparison, with 2 kg perhectare of chloroacetic acid- N-isopropylanilide (II), each activeingredient being dispersed in 500 liters of water per hectare.

After 4 to 5 weeks it was ascertained that active ingredient I had thesame good crop plant compatibility as H, combined with a strongerherbicidal action.

The results of this experiment are given below:

On an agricultural plot the plants Zea mays, Gossypium hirsutum, Sojahispida, Beta vulgaris, Echinochloa crus-galli, Digitaria sanguinalis,Panicum virgatum, Eleusine indica and Poa annua were treated at a growthheight of 2 to 14 cm with 2 kg per hectare of l and 2 kg per hectare ofII, each active ingredient being emulsified in 500 liters of water perhectare.-

After 3 to 4 weeks it was ascertained that active ingredient I had notonly better crop plant compatibility than 11, but also a strongerherbicidal action.

The results of this experiment are given below:

Active ingredient I ll Zea mays 0 0 Gossypium hirrulum 0 l5 Soja hixpida5 1'5 Bela vulgaris 0 l0 Erhinochloa crux-gall! 60 Digilaria sanguinalis40 Panicum virgalum 90 4O Eleusine indica 9O 30 Poa annua 80 I5 0 nodamage complete destruction The action of the following compoundscorresponds to that of I above:

O-(isopropylaminosulfonyl)-glycolic acid-N- methylanilideO-(isopropylaminosulfonyl)-glycolic acid-N- isobutylanilide 7O-(ethylaminosulfonyl)-glycolic acid-N-butyn-l-yl- 3-anilideO-(isopropylaminosulfonyl)-glycolic acidN-secbutylanilide EXAMPLE 4 90parts by weight of compound I is mixed with 10 parts by weight ofN-methyl-a-pyrrolidone. A mixture is obtained which is suitable forapplication in the form of very fine drops.

EXAMPLE 5 20 parts by weight of compound I is dissolved in a mixtureconsisting of 80 parts by weight of xylene, parts by weight of theadduct of 8 to 10 moles of ethylene oxide to 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide to 1 mole of castor oil. By pouring the solutioninto 100,000 parts by weight of water and uniformly distributing ittherein, an aqueous dispersion is obtained containing 0.02% by weight ofthe active ingredient.

EXAMPLE 6 parts by weight of compound I is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 7 moles of ethyleneoxide to 1 mole of isooctylphenol, and 10 parts by weight of the adductof 40 moles of ethylene oxide to 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02% by weight of the active ingredient.

EXAMPLE 7 20 parts by weight of compound I is dissolved in a mixtureconsisting of parts by weight of cyclohexanol, 65 parts by weight of'amineral oil fraction having a boiling point between 210 and 280C, and 10parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole ofcastor oil. By pouring the solution into 100,000 parts by weight ofwater and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound I is well mixed withthalene-a-sulfonic acid, 17 parts by weight of the sodium salt ofaligninsulfonic acid obtained from a sulfite waste liquor, and parts byweight of powdered silica gel, and triturated in a hammer mill. Byuniformly distributing the mixture in 20,000 parts by weight of water, aspray liquid is obtained containing 0.1% by weight of the activeingredient.

EXAMPLE 9 3 parts by weight of compound I is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

EXAMPLE 10 30 parts by weight of compound I is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

EXAMPLE 1 l acid-N- VII O-(isopropylaminosulfonyl)-glycolic acidN-ethylanilide VIII O-(ethylaminosulfonyl)-glycolic acid-N- ethylanilideAfter 3 weeks it was ascertained that the active ingredients exhibitedgood crop plant compatibility combined with an excellent herbicidalaction.

3 parts by weight of the sodium salt of diisobutylnaph- 50 The resultsare given below:

Active ingredient I III IV V VI VII VIII Crop plants: Saja hirpida O 5 00 0 0 O Gosxypium hirrulum O O 0 O O O 0 Beta vulgaris 0 (l 0 0 (l 0 0Brasxiza napux 0 O 0 O 0 O 0 Helium/lax annuux 0 0 O O 0 0 0 Allium cepa0 0 O O O O O Spinucia olz'mcea 0 0 0 O 0 O 0 lisum .s'arirum O 0 0 O O0 O Unwanted plants: Ecllilmchlua cruxgalli 95 I00 95 95 I00 I00 95Digimria sanguinalis 95 100 95 I00 90 Sclaria faherii 95 I00 95 90 95 95P00 annua I00 I00 100 I00 I00 I00 95 Lolium mu/liflorum I00 I00 95 95I00 I00 95 Eleuxine indica 100 I00 95 90 100 95 9O Malricaria clmmomilla80 90 SI) 80 90 80 75 0 no damage 100 complete destruction EXAMPLE 12l-yl-3-anilide Vll O-(isopropylaminosulfonyl)-glycolic acid-N-ethylanilidc Vlll O-(ethylaminosulfonyl)-glycolic acid-N- ethylanilide.

After 3 weeks it was ascertained that the active ingredients exhibitedfavorable crop plant compatibility combined with a good herbicidalaction.

The results are given below:

O-(isopropylaminosulfonyl)-glycolic ethylanilideO-(isopropylaminosulfonyl)-glycolic acid-N-propargylanilideO-(pentylaminosulfonyl)-glycolic acid-N-butyn-l-yl- 3-anilideO-(aminosulfonyl)-glycolic acid-N-methylanilide We claim:

1. A process for controlling the growth of unwanted plants wherein thesoil in which unwanted growth is to be prevented is treated with aherbicidally effective amount of a substitutedO-(aminosulfonyl)-glycolic anilide of the formula acid-N- where Rdenotes hydrogen, alkyl of l to 6 carbon atoms, haloalkyl of l to 6carbon atoms, cyclopentyl, or cyclohexyl, R denotes phenyl, and Rdenotes a member selected from the group consisting of methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertbutyl, pentyl,cyclopentyl, hexyl, cyclohexyl, allyl, butenyl, pentenyl, hexenyl,propargyl, butynyl, pentynyl, or benzyl.

2. A process for controlling the growth of unwanted plants wherein saidunwanted plants are treated with a Active ingredient I III IV V VI VIIVIII Crop plants:

Soja llixpida 0 0 0 0 5 0 Beta vulgaris O 0 O 0 O 0 O (iassypiumlrirxulum 0 0 O O 0 O O Oryza .s'ativa 5 5 5 5 Trilirum aariivum l0 5 55 5 l0 5 Zea mayx O 0 0 0 0 5 0 Unwanted plants:

Alopecurux myoxumides 90 95 85 90 95 90 Lolium mulnflorum 90 95 80 80 90Sz'mriu fuberii I00 90 90 90 95 95 Eleuxim' indicu 85 95 90 8O 85 9O 90Ethinochloa crux-gum 75 95 90 9O 8O 8O 85 Cln'nnpndium album 80 90 70 7070 80 75 Malric'aria chanmmilla 80 90 75 75 70 8O 80 0 no damagecomplete destructionacid-N-tertacid-N-methylaniacid-N-nacid-N-nacid-N-secherbicidallyeffective amount of a substituted 0- (aminosulfonyl)-glycolic anilide ofthe formula where R denotes hydrogen, alkyl of l to 6 carbon atoms,haloalkyl of l to 6 carbon atoms, cyclopentyl, or cyclohexyl, R denotesphenyl, and R denotes a member selected from the group consisting ofmethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tertbutyl, pentyl, cyclopentyl, hexyl, cyclohexyl, allyl, butenyl,pentenyl, hexenyl, propargyl, butynyl, pentynyl, or benzyl.

1. A PROCESS FOR CONTROLLING THE GROWTH OF UNWANTED PLANTS WHEREIN THESOIL IN WHICH UNWANTED GROWTH IS TO BE PREVENTED IS TREATED WITH AHERBICIDAL EFFECTIVE AMOUNT OF A SUBSTITUTED O-(AMINOSULFONYL)-GLYCOLICANILIDE OF THE FORMULA
 2. A process for controlling the growth ofunwanted plants wherein said unwanted plants are treated with aherbicidally effective amount of a substitutedO-(aminosulfonyl)-glycolic anilide of the formula